Naphthophenazine dye



. known manner the free amino-group may be Patented Aug. 23, 1932 OFF-Ice GUSTAV REDDELEEN, OFLEIPZIG, AND HEINRICH OHLENDORF, OF DESSAU IN ANHALT, GERMANY, ASSIGNOBS TO GENERAL ANILINE WORKS, INC., OF NEW YORK, N. Y.,

A CORPORATION OF- DELAWARE narrrrnorfinivazmn DYE No Drawing. Applicationpfiled February 15,

substituted in the 1-position by a group X comprising OH, NH "and NH-acyl. The.

new dyes in the form of dry sodium salts are yellow to orange powders, soluble with a yellow to orange color in water.

The dyes may be manufactured by condensing a 1LQ-naphthocjuinone-sulfonic acid substituted in the 8-position by a group comprising OH, NH and NH-acyl with an 1.2- diamino-compound of. the benzene series such as 1.2-diaminobenzene, 1-methyl-3Ardiaminobenzene, 1-chloro-3. l-diaminobenzene, 1.2 diarninobenzeneA-sulfonic acid. In .a

acylated and from an acyl-amino-group the acid radicle may be split ofi'. l/Vhen starting from the condensation product of a 1.2- napthoquinone-disulfonic acid containing in the 8-position a sulfonic acid group with a 1.2-diamino-compound of the benzene series the sulfonic acid group in the 1-position of. the napthophenazine nucleus is replaced bythe hydroXyl-group in the alkali melt, the other sulfonic acid group being retained.

The following examples, the parts being by weight, illustrate 'theinvention without limiting it: Y 7 v 7 Example 1.10 parts of a. B-naphthophenazine-1.6-disulfonic acid, which may be made irom l2-naphthoquinone-8.S-disulfonic acid and1.2-diaminobenzene, are stirred with 15 parts of a solution or potassium hydroxide of 48 per cent. strength, whereupon 'parts of potassium'hydroxide are added and the whole is kept at 170 C. for about an hour.

1929, Serial No. 340,324, and in Germany February. 7, 1928.

During this operation hydroxylenters the 1- positiomwhile the sulfonic acidgrioup in the; 6-po'sitiofn is retained. The melt isdiliited with .120 parts of waterlOn cooling, the potassium salt of l-hydroxy-a.fl-naphthophenazine-6-sulfonic acid v separates, while the mother-liquor contains acid (obtainable,for example", by reducing in known manner the nitroso-cornpound"of'8 acetylainino l-hydroxynaphthalene-5-sulfonic acid to produce 8-acetylamino-2-aminod hydroXynaphthal-ene-5-sulfonic acid and oxidizing the latter) are condensed in the usual manner with 11 parts of 1.2-diaminobenzene. The potassium 1'-acetylamino-u.,8- naphthophenazine-4esulfonate i 1 OHQAIJOT j thus obtained crystallizes. in yellow, brassy needles, soluble in water to a greenish-yellow solution and in'concentrated sulfuric'acid' to a green-yellow solution. I-tfdyes wool a clear greenish-yellow tint of excellent levelling power and-unusually high fastness tolightl Ema-mple 3. 38 partsofthe sodiurnisalt of the acetyl-con ipound, m'ade as fdescrib d, in

Example 2, are dissolved in 800 parts of water and, after addition of 100 parts of concentrated sulfuric acid, the solution is boiled for 6 hours, whereby the 1-a1nino-u.,8-naphthophenazine-4-sulfonic acid Oib is' precipiated in the form of blue needles, it being very sparingly soluble inits free state. It yields an'orange alkalisalt soluble V in watent It dyes wool a red-orange tint of crystallizes in yellow: needles. It dyes wool a reddish-yellow tint of good fastnessto washing and fulling and excellent fastness to light.

Thecompound obtained in corresponding manner from 2-chlorobenZoyl-chl0ride yields an orange dyeing which has good fastness to Washing and fulling and marked levelling power. x

- The dyestufi' from 4-nitrobenzoyl-chloride, made in similar manner, yields, like the acetyl-compound, clear greenishyellow tints. Besides the marked levelling power of the dyestufi' the dyeing has an excellent fastness 'to washing and fulling, as well as an unusually 7 high degree of fastness to light. Similar clear yellow tints'are obtained with the dyestuff made from 8-nitrobenzoylchloride. a

E wample 5. parts of the potassium salt of 8-acetyl'amino-1.2-naphthoquinione-5-sulfonic acid (Example 2) are condensed, at

'ZO80 (l, in 1000 parts of water with 40 parts of 1.2-diami'nobenzenel-sulfonic acid with addition of {L2 parts of crystallized sodiumacetate. When the reaction is complete the azine compound isprecipitated' by addition of common salt. This precipitate i,873,9ss

is a mixture of 1-acetylamino-a.,8-naphtho= phenazine-4L9-dissulfonic acid In dry conditionit is a yellow powder, which vdissolves in water to a yellow solution. It dyes wool a pure yellow of good fastness to washing and fulling, as well as of excellent fastness to light.

Saponification of this product in the manner prescribed in Example 3 yields a 1- amino-a./3-naphthophenazine-disulfonic acid which may be acylated, again by means of a suitable acid chloride toproduce a l aroylamino-azine-disulfonic acid. For example, with d-nitrobenzoyhchloride there is obtained a dyestuti which dyes animal fiber very clear yellow tints which have properties of fastness even better than those of the acetyl-compound. r

\ Example 6.In the manner described in Example 2, 8-acetylamino-1.Q-naphthoquin one-L-sulfonic acid (obtainable from 8-acetylamino 1 hydroxynaphthalene 4; sulfonic acid) is condensed with 1.2-diaminobenzene. The 1eacetylamino-a.,8-naphthophenazine-5- sulfonic acid thus obtained OHa-CO dyes Wool tints ofsimilar color and fas'tness to those described in ExampleQ for the corresponding l-sulfonic acid,

By saponification there may be obtained a 1-amino-a.,8-naphthophenazine 5 sulfonic acid which by treatment with an acid chloride, such as benzoylchloride, or a ch'lorinated or nitrated benzoylchloride, gives further dyestuffs which are similar tothose obtained as described in Examples 4 and .5. J

lVe claim: V

nave-pas 1 As a new product, the azine dye of the general formula O0 O-ENVW being in the form of the sodium salt being a yellow compound crystallized in yellow needles, soluble in water with a yellow color and dyeing wool fast yellow tints.

2. As new products, the azine dyes corresponding in the form of the free acids to the probable, general formula wherein X represents OH, NH NH-acetyl, NH-benzoyl, NH-halogenobenzoyl or NH- nitrobenzoyl and n is 1 or 2, these dyes being in the form of the sodium salts yellow to orange powders soluble in water with a yellow to orange color and dyeing wool fast yellow to orange tints. V

4. As new products, the azine dyes corresponding in the form of the free acids to the probable, general formula wherein n is l or 2, these dyes being in the form of the sodium salts yellow to orange powders soluble in water with a yellow to orange color and dyeing wool fast yellow to orange tints.

5. As new-products; the azine dyes corresponding in the form of the free acidst'o" the probable, generalformula' wherein Y represents a benzoyl, a nitrobenzoyl or a halogeno benzoyl group and? is 1 or 2, ,thesedyesbeingin the form oftthe sodium salts yellow to vorange powders solu ble in water with a yellow to orange'color and dyeing wool fast yellow to orange tints.

6. As new products, the azine dyes corresponding 1n the form'ofthe free 'acids to the general formula;

it I

wherein X represents an amino group an acetylamino, benzoylam1no,a nitrobenzoylamino or a halogenobenzoyl amino group,

these dyes" beinginthe' form of the sodium salts yellow to orange powders soluble in water with a yellow to orange color and dyeing wool fast yellow to orange tints.

7, As new products, the azine dyes corresponding in the form of the free acids to the general formula these dyes being in the form of the sodium salts yellow to orange powders soluble in water with a yellow to orange color and dyeing wool fast yellow to orange tints.

its

8. As new products, the azine dyes corresponding in the form of the free acids to the general formula YHN @TIEDfiom wherein Y is a benzoyl, a nitrobenzoyl or a halogeno benzoyl group, these dyes being in the form of the sodium salts yellow to orange powders soluble in water with a yellow to orange color and dyeing wool fastyellow to orange tints.

9. As anew product, the azine dye corresponding in the form of the formula V this dye being in the form of the sodium salt a yellow poWder'soluble in water With a yellow color and dyeing W001 clear greenish-yellow tints. e I 4 I 10. As a new product, the azine dye corresponding in the form of the free acid to the formula v u l w free acid to the this dye being in the form of the sodium salt an orange powder soluble in Water With an orange color and dyeing Wool clear orange tints. i

In "testimony whereof we afilx our signaturesi' GUSTAV REDDELIEN. HEINRICH OHLENDORR SOaH 

